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- ItemFusion of MALDI Spectrometric Imaging and Raman Spectroscopic Data for the Analysis of Biological Samples(Lausanne : Frontiers Media, 2018) Ryabchykov, Oleg; Popp, Jürgen; Bocklitz, Thomas W.Despite of a large number of imaging techniques for the characterization of biological samples, no universal one has been reported yet. In this work, a data fusion approach was investigated for combining Raman spectroscopic data with matrix-assisted laser desorption/ionization (MALDI) mass spectrometric data. It betters the image analysis of biological samples because Raman and MALDI information can be complementary to each other. While MALDI spectrometry yields detailed information regarding the lipid content, Raman spectroscopy provides valuable information about the overall chemical composition of the sample. The combination of Raman spectroscopic and MALDI spectrometric imaging data helps distinguishing different regions within the sample with a higher precision than would be possible by using either technique. We demonstrate that a data weighting step within the data fusion is necessary to reveal additional spectral features. The selected weighting approach was evaluated by examining the proportions of variance within the data explained by the first principal components of a principal component analysis (PCA) and visualizing the PCA results for each data type and combined data. In summary, the presented data fusion approach provides a concrete guideline on how to combine Raman spectroscopic and MALDI spectrometric imaging data for biological analysis.
- ItemFluorosolvatochromism of furanyl- and thiophenyl-substituted acetophenones(London : RSC, 2015) Friebe, Nadine; Schreiter, Katja; Kübel, Joachim; Dietzek, Benjamin; Moszner, Norbert; Burtscher, Peter; Oehlke, Alexander; Spange, StefanA series of para-substituted acetophenones bearing a furanyl or a thiophenyl moiety show a large Stokes-shift, which is a function of various solvent properties. Photophysical properties such as emission lifetime of the compounds have been determined using time-correlated-single photon counting to secure the intrinsic fluorescence behaviour. The solvent dependent position of the UV/Vis emission band [small nu, Greek, tilde]max,em of the compounds has been measured in 26 various solvents. The influence of the solvent on [small nu, Greek, tilde]max,em is of very complex nature and mathematically analysed by multiple square linear solvation energy (LSE)-correlation analysis using Catalán's four-solvent parameter set. Solvent acidity has a strong influence on the bathochromic shift of 2,5-disubstituted furan derivatives compared to the non-5-substituted furan and thiophene derivatives, which show a contrary behaviour. Therefore, the 5-cyanofuranyl-substituted acetophenone derivative is useful as a probe for measuring environmental properties by fluorescence spectroscopy.
- ItemDifferent storage conditions influence biocompatibility and physicochemical properties of iron oxide nanoparticles(Basel : Molecular Diversity Preservation International (MDPI), 2015) Zaloga, Jan; Janko, Christina; Agarwal, Rohit; Nowak, Johannes; Müller, Robert; Boccaccini, Aldo R.; Lee, Geoffrey; Odenbach, Stefan; Lyer, Stefan; Alexiou, ChristophSuperparamagnetic iron oxide nanoparticles (SPIONs) have attracted increasing attention in many biomedical fields. In magnetic drug targeting SPIONs are injected into a tumour supplying artery and accumulated inside the tumour with a magnet. The effectiveness of this therapy is thus dependent on magnetic properties, stability and biocompatibility of the particles. A good knowledge of the effect of storage conditions on those parameters is of utmost importance for the translation of the therapy concept into the clinic and for reproducibility in preclinical studies. Here, core shell SPIONs with a hybrid coating consisting of lauric acid and albumin were stored at different temperatures from 4 to 45 °C over twelve weeks and periodically tested for their physicochemical properties over time. Surprisingly, even at the highest storage temperature we did not observe denaturation of the protein or colloidal instability. However, the saturation magnetisation decreased by maximally 28.8% with clear correlation to time and storage temperature. Furthermore, the biocompatibility was clearly affected, as cellular uptake of the SPIONs into human T-lymphoma cells was crucially dependent on the storage conditions. Taken together, the results show that the particle properties undergo significant changes over time depending on the way they are stored.
- ItemHole injection dynamics from two structurally related Ru-bipyridine complexes into NiOx is determined by the substitution pattern of the ligands(Cambridge : RSC Publ., 2015) Bräutigam, Maximilian; Kübel, Joachim; Schulz, Martin; Vos, Johannes G.; Dietzek, BenjaminThe dyes bis[2,2′-bipyridine][4,4′-dicarboxy-2,2′-bipyridine]ruthenium(II) dihexafluorophosphate, [Ru(bpy)2dcb](PF6)2 (Ru1), and tris[4,4′-bis(ethylcarboxy)-2,2′-bipyridine]ruthenium(II) dihexafluorophosphate, [Ru(dceb)3](PF6)2 (Ru2), attached to NiOx nanoparticle films were investigated using transient absorption and luminescence spectroscopy. In acetonitrile solution the dyes reveal very similar physical and chemical properties, i.e. both dyes exhibit comparable ground state and long-lived, broad excited state absorption. However, when immobilized onto a NiOx surface the photophysical properties of the two dyes differ significantly. For Ru1 luminescence is observed, which decays within 18 ns and ultrafast transient absorption measurements do not show qualitative differences from the photophysics of Ru1 in solution. In contrast to this the luminescence of photoexcited Ru2 on NiOx is efficiently quenched and the ultrafast transient absorption spectra reveal the formation of oxidized nickel centres overlaid by the absorption of the reduced dye Ru2 with a characteristic time-constant of 18 ps. These findings are attributed to the different localization of the initially photoexcited state in Ru1 and Ru2. Due to the inductive effect (−I) of the carboxylic groups, the lowest energy excited state in Ru1 is localized on the dicarboxy-bipyridine ligand, which is bound to the NiOx surface. In Ru2, on the other hand, the initially populated excited state is localized on the ester-substituted ligands, which are not bound to the semiconductor surface. Hence, the excess charge density that is abstracted from the Ru-ion in the metal-to-ligand charge-transfer transition is shifted away from the NiOx surface, which ultimately facilitates hole transfer into the semiconductor.
- ItemOnline investigation of respiratory quotients in Pinus sylvestris and Picea abies during drought and shading by means of cavity-enhanced Raman multi-gas spectrometry(Cambridge : Soc., 2015) Hanf, Stefan; Fischer, Sarah; Hartmann, Henrik; Keiner, Robert; Trumbore, Susan; Popp, Jürgen; Frosch, TorstenPhotosynthesis and respiration are major components of the plant carbon balance. During stress, like drought, carbohydrate supply from photosynthesis is reduced and the Krebs cycle respiration must be fueled with other stored carbon compounds. However, the dynamics of storage use are still unknown. The respiratory quotient (RQ, CO2 released per O2 consumed during respiration) is an excellent indicator of the nature of the respiration substrate. In plant science, however, online RQ measurements have been challenging or even impossible so far due to very small gas exchange fluxes during respiration. Here we apply cavity-enhanced multi-gas Raman spectrometry (CERS) for online in situ RQ measurements in drought-tolerant pine (Pinus sylvestris [L.]) and drought-intolerant spruce (Picea abies [L. H. Karst]). Two different treatments, drought and shading, were applied to reduce photosynthesis and force dependency on stored substrates. Changes in respiration rates and RQ values were continuously monitored over periods of several days with low levels of variance. The results show that both species switched from COH-dominated respiration (RQ = 1.0) to a mixture of substrates during shading (RQ = 0.77–0.81), while during drought only pine did so (RQ = 0.75). The gas phase measurements were complemented by concentration measurements of non-structural carbohydrates and lipids. These first results suggest a physiological explanation for greater drought tolerance in pine. CERS was proven as powerful technique for non-consumptive and precise real-time monitoring of respiration rates and respirational quotients for the investigation of plant metabolism under drought stress conditions that are predicted to increase with future climate change.
- ItemSPION@polydehydroalanine hybrid particles(London : RSC Publishing, 2015) von der Lühe, Moritz; Günther, Ulrike; Weidner, Andreas; Gräfe, Christine; Clement, Joachim H.; Dutz, Silvio; Schacher, Felix H.It is generally accepted that a protein corona is rapidly formed upon exposure of nanoparticles to biological fluids and that both the amount and the composition of adsorbed proteins affect the dispersion properties of the resulting particles. Hereby, the net charge and overall charge density of the pristine nanoparticles are supposed to play a crucial role. In an attempt to control both charge and charge distribution, we report on the coating of superparamagnetic iron oxide nanoparticles (SPIONs) with different polyelectrolytes. Starting from orthogonally protected polydehydroalanine, the material can be easily transformed into a polyanion (poly(tert-butoxycarbonyl acrylic acid), PtBAA), polycation (poly(aminomethylacrylate), PAMA), or even a polyzwitterion (polydehydroalanine, PDha). While coating of SPIONs with PtBAA and PDha was shown to be successful, approaches using PAMA have failed so far. The dispersion properties of the resulting hybrid particles have been investigated using dynamic light scattering (DLS), zeta-potential, and TEM measurements – the amount of adsorbed polymer was quantified using vibrating sample magnetometry (VSM) and thermogravimetric analysis (TGA).
- ItemMicrobial respiration and natural attenuation of benzene contaminated soils investigated by cavity enhanced Raman multi-gas spectroscopy(Cambridge : Soc., 2015) Jochum, Tobias; Michalzik, Beate; Bachmann, Anne; Popp, Jürgen; Frosch, TorstenSoil and groundwater contamination with benzene can cause serious environmental damage. However, many soil microorganisms are capable to adapt and are known to strongly control the fate of organic contamination. Innovative cavity enhanced Raman multi-gas spectroscopy (CERS) was applied to investigate the short-term response of the soil micro-flora to sudden surface contamination with benzene regarding the temporal variations of gas products and their exchange rates with the adjacent atmosphere. 13C-labeled benzene was spiked on a silty-loamy soil column in order to track and separate the changes in heterotrophic soil respiration – involving 12CO2 and O2 – from the natural attenuation process of benzene degradation to ultimately form 13CO2. The respiratory quotient (RQ) decreased from a value 0.98 to 0.46 directly after the spiking and increased again within 33 hours to a value of 0.72. This coincided with the maximum 13CO2 concentration rate (0.63 μmol m−2 s−1), indicating the highest benzene degradation at 33 hours after the spiking event. The diffusion of benzene in the headspace and the biodegradation into 13CO2 were simultaneously monitored and 12 days after the benzene spiking no measurable degradation was detected anymore. The RQ finally returned to a value of 0.96 demonstrating the reestablished aerobic respiration.
- ItemIn situ spectroelectrochemical and theoretical study on the oxidation of a 4H-imidazole-ruthenium dye adsorbed on nanocrystalline TiO2 thin film electrodes(Cambridge : RSC Publ., 2015) Zhang, Ying; Kupfer, Stephan; Zedler, Linda; Schindler, Julian; Bocklitz, Thomas; Guthmuller, Julien; Rau, Sven; Dietzek, BenjaminTerpyridine 4H-imidazole-ruthenium(II) complexes are considered promising candidates for use as sensitizers in dye sensitized solar cells (DSSCs) by displaying broad absorption in the visible range, where the dominant absorption features are due to metal-to-ligand charge transfer (MLCT) transitions. The ruthenium(III) intermediates resulting from photoinduced MLCT transitions are essential intermediates in the photoredox-cycle of the DSSC. However, their photophysics is much less studied compared to the ruthenium(II) parent systems. To this end, the structural alterations accompanying one-electron oxidation of the RuIm dye series (including a non-carboxylic RuIm precursor, and, carboxylic RuImCOO in solution and anchored to a nanocrystalline TiO2 film) are investigated via in situ experimental and theoretical UV-Vis absorption and resonance Raman (RR) spectroelectrochemistry. The excellent agreement between the experimental and the TDDFT spectra derived in this work allows for an in-depth assignment of UV-Vis and RR spectral features of the dyes. A concordant pronounced wavelength dependence with respect to the charge transfer character has been observed for the model system RuIm, and both RuImCOO in solution and attached on the TiO2 surface. Excitation at long wavelengths leads to the population of ligand-to-metal charge transfer states, i.e. photoreduction of the central ruthenium(III) ion, while high-energy excitation features an intra-ligand charge transfer state localized on the 4H-imidazole moiety. Therefore, these 4H-imidazole ruthenium complexes investigated here are potential multi-photoelectron donors. One electron is donated from MLCT states, and additionally, the 4H-imidazole ligand reveals electron-donating character with a significant contribution to the excited states of the ruthenium(III) complexes upon blue-light irradiation.
- ItemLinear and non-linear optical imaging of cancer cells with silicon nanoparticles(Basel : Molecular Diversity Preservation International (MDPI), 2016) Tolstik, Elen; Osminkina, Liubov A.; Akimov, Denis; Gongalsky, Maksim B.; Kudryavtsev, Andrew A.; Timoshenko, Victor Yu.; Heintzmann, Rainer; Sivakov, Vladimir; Popp, JürgenNew approaches for visualisation of silicon nanoparticles (SiNPs) in cancer cells are realised by means of the linear and nonlinear optics in vitro. Aqueous colloidal solutions of SiNPs with sizes of about 10–40 nm obtained by ultrasound grinding of silicon nanowires were introduced into breast cancer cells (MCF-7 cell line). Further, the time-varying nanoparticles enclosed in cell structures were visualised by high-resolution structured illumination microscopy (HR-SIM) and micro-Raman spectroscopy. Additionally, the nonlinear optical methods of two-photon excited fluorescence (TPEF) and coherent anti-Stokes Raman scattering (CARS) with infrared laser excitation were applied to study the localisation of SiNPs in cells. Advantages of the nonlinear methods, such as rapid imaging, which prevents cells from overheating and larger penetration depth compared to the single-photon excited HR-SIM, are discussed. The obtained results reveal new perspectives of the multimodal visualisation and precise detection of the uptake of biodegradable non-toxic SiNPs by cancer cells and they are discussed in view of future applications for the optical diagnostics of cancer tumours.
- ItemA Machine Learning-Based Raman Spectroscopic Assay for the Identification of Burkholderia mallei and Related Species(Basel : MDPI, 2019) Silge, Anja; Moawad, Amira A.; Bocklitz, Thomas; Fischer, Katja; Rösch, Petra; Roesler, Uwe; Elschner, Mandy C.; Popp, Jürgen; Neubauer, HeinrichBurkholderia (B.) mallei, the causative agent of glanders, and B. pseudomallei, the causative agent of melioidosis in humans and animals, are genetically closely related. The high infectious potential of both organisms, their serological cross-reactivity, and similar clinical symptoms in human and animals make the differentiation from each other and other Burkholderia species challenging. The increased resistance against many antibiotics implies the need for fast and robust identification methods. The use of Raman microspectroscopy in microbial diagnostic has the potential for rapid and reliable identification. Single bacterial cells are directly probed and a broad range of phenotypic information is recorded, which is subsequently analyzed by machine learning methods. Burkholderia were handled under biosafety level 1 (BSL 1) conditions after heat inactivation. The clusters of the spectral phenotypes and the diagnostic relevance of the Burkholderia spp. were considered for an advanced hierarchical machine learning approach. The strain panel for training involved 12 B. mallei, 13 B. pseudomallei and 11 other Burkholderia spp. type strains. The combination of top- and sub-level classifier identified the mallei-complex with high sensitivities (>95%). The reliable identification of unknown B. mallei and B. pseudomallei strains highlighted the robustness of the machine learning-based Raman spectroscopic assay. © 2019 by the authors